Ampholytic, fluorine-containing esters of phosphorous acid

ABSTRACT

Compounds of the formula ##STR1## wherein R f  is a perfluoroalkyl group of 3 to 16 carbon atoms, R 1  and R 2  is hydrogen, lower alkyl of 1 to 4 carbon atoms, cyclohexyl, 2-hydroxyalkyl, or R f  --(CF═CH) m  --(CH 2 ) p  --, Q is --(CH 2 ) x  --, --CH 2  CHR--, or --CH 2  --CRR&#39;--CH 2  -- (R is lower alkyl or phenyl, R&#39; is lower alkyl, phenyl or hydrogen), x is an integer of 2 or 3, m is an integer of 0 or 1 and p is an integer of 1 to 4, are prepared by reacting florinated amines of the formula 
     
         R.sub.4 --(CF═CH).sub.m --(CH.sub.2).sub.p --NR.sub.1 R.sub.2 
    
     with cyclic phosphites of the formula ##STR2## these compounds are useful for lowering the surface tension in aqueous solutions and as wetting agents in dry-cleaning processes for textiles.

The invention relates to ampholytic, fluorine-containing esters ofphosphorous acid of the general formula ##STR3## in which R_(f)represents a perfluoroalkyl radical having 3 to 16 C atoms, R₁ and R₂which can be identical or different represent hydrogen atoms,short-chain alkyl radicals having 1 to 4 C atoms, cyclohexyl radicals,2-hydroxyalkyl radicals or the radical R_(f) --(CF═CH)_(m) --(CH₂)_(p)and Q represents alkylene radicals --(CH₂)_(x) -- with x = 2 or 3 andalkylene radicals --CH₂ CHR-- or --CH₂ CRR'--CH₂ -- with R and R' beinga short-chain alkyl radical or a phenyl radical, it also being possiblefor R' to be H, and in which, furthermore, m is 0 or 1 and p is aninteger from 1 to 4.

In the general formula indicated above, R_(f) preferably represents aperfluoroalkyl radical having 5 to 12 C atoms, and straight-chainperfluoroalkyl radicals are particularly preferred. R₁ and R₂ which canbe identical or different are preferably straight-chain alkyl radicalshaving 1 to 4, in particular 1 to 2, C atoms, and also the2-hydroxyethyl radical, one of the two radicals R₁ to R₂ beingespecially a 2-hydroxyethyl radical. R₁ or R₂ can also preferably denotea radical of the formula R_(f) (CF═CH)_(m) --(CH₂)_(p), and p herepreferably is an integer from 1 to 3 and m can be 1 or preferably 0. ForQ, in addition to radicals of the structure --(CH₂)_(x) -- with x = 2 or3, those of the structure --CH₂ CHR-- and --CH₂ CRR'--CH₂ -- arepreferred in which R and R' are an alkyl radical having 1 to 2 C atomsand, in particular, are a methyl radical. Preferably, R' can also be aphenyl radical. The index p preferably assumes integral values from 1 to3.

The invention also relates to a process for the manufacture ofampholytic, fluorine-containing esters of phosphorous acid of theabovementioned general formula I, in which R_(f), R₁, R₂, Q, m and phave the abovementioned meaning (also with respect to the preferredlimits), in which process amines of the general formula

    R.sub.f --(CF═CH).sub.m --(CH.sub.2).sub.p --NR.sub.1 R.sub.2

in which R_(f), R₁, R₂, m and p have the abovementioned meaning, arereacted with cyclic phosphites of the general formula ##STR4## in whichQ has the abovementioned meaning, at temperatures between +20° C. and+140° C., in bulk or in the presence of polar solvents. In particular,this process according to the invention is carried out with amines ofthe abovementioned formula and cyclic phosphites of the abovementionedformula, in which R_(f), R₁, R₂, Q, m and p have the preferred meaningmentioned.

The said reaction is advantageously carried out at a temperature between+20° and +140° C., preferably between +60° and +140° C. It isappropriate here to initially introduce the fluorine-containing amine,warmed to the reaction temperature, and slowly to add the cyclicphosphorous acid ester, used as the alkylating agent, until the amountsare in an equimolar ratio. It is also advisable to blanket the reactionmixture with an inert gas, such as, for example, nitrogen. The reactionis preferably carried out under normal pressure, but it is also possibleto operate under reduced pressure or, especially in the presence ofsolvents, under a slightly elevated pressure. In principle, the reactiondoes not require a solvent. However, for easier handling of the startingmaterials and end products, which are very viscous at room temperature,it is advantageous to add polar solvents which appropriately are capableof dissolving both the starting materials and the end products. Polarsolvents, such as methanol, ethanol, isopropanol, methylene chloride,chloroform as well as glycol and dimethyl glycol are particularlysuitable. At the reaction temperatures of +60° to +120° C., which aregenerally used, the reaction has ended after about 2 to 4 hours. Toincrease the conversion and the reaction rate, it has proved to beparticularly advantageous to add a relatively small amount of water,preferably 1 to 10 mole %, to the reaction process.

The fluorinated amines employed as the starting compounds can bemanufactured, for example, in accordance with U.S. Pat. No. 3,535,381,U.S. Pat. No. 3,257,407, DT-OS No. 2,141,542 or DT-OS No. 1,768,939. Forthe further reaction with the cyclic esters of phosphorous acid, it isalso possible successfully to employ mixtures of saturated andunsaturated fluorinated amines of the abovementioned formula, that is tosay those amines in which m is 0 or 1. The cyclic esters of phosphorousacid, used as the further reaction component, are readily accessiblefrom the corresponding 1,2- or 1,3-glycols and phosphorus trichloride bymethods which are generally known (compare Houben-Weyl, Methoden derorganischen Chemie, [Methods of Organic Chemistry], 4th edition, volume12; 2, page 25 to 26). They can also be obtained directly bytransesterification of dialkyl phosphites with the corresponding glycols(ibid. page 35 to 36).

The resulting yields of ampholytic, fluorine-containing esters ofphosphorous acid according to the invention, of the formula I, arevirtually quantitative and most of these compounds are excellentlysoluble in water. The solvent which may have been added can be separatedoff by distillation, if necessary under reduced pressure. In many cases,however, this is unnecessary since the compounds according to theinvention are employed in the dissolved form, if necessary with theaddition of water.

The examples which follow illustrate the manufacture of the compoundsaccording to the invention:

EXAMPLE 1

399.2 g = 1.0 mole of C₅ F₁₁ CF═CH--CH₂ --N(C₂ H₅)₂, 500 ml ofisopropanol and 5 ml of water are initially introduced into a glassflask which is equipped with a stirrer, reflux condenser, droppingfunnel and thermometer, the mixture is heated up to the boiling point ofisopropanol and 150.1 g (= 1.0 mole) of a cyclic phosphite of theformula ##STR5## are then added in the course of 20 minutes. Thereaction mixture is then boiled under reflux for a further 4 hours.After the reaction has ended, the isopropanol is distilled off and evensmall residual amounts of the solvent are removed by applying a waterpump vacuum. This gives a light brown oil which is highly viscous atroom temperature and which is soluble in water giving a clear solution.

Yield: 545.6 g = 99.3% of theory.

The nuclear magnetic resonance spectra of the substance showed thefollowing signals:

¹ H nuclear magnetic resonance spectrum (measured here and in thefurther examples using a 60 MHz instrument from Messrs. Japan ElectronOptics Co. Ltd. at 25° C., with tetramethylsilane as an internalstandard; the signals are indicated in ppm in accordance with the δscale) in d₄ -methanol:

    ______________________________________                                         ##STR6##       doublet with a coupling constant  of ˜629 Hz            5.7 to 6.8: CFCH                                                                              triplettized doublet                                           ##STR7##        multiplet                                                    3.7 to 4.1: HO.sub.2 POCH.sub.2                                                               multiplet                                                      ##STR8##       superimposing multiplets                                       ##STR9##       triplet                                                        ##STR10##      singlet                                                       ______________________________________                                    

¹⁹ F nuclear magnetic resonance spectrum (measured here and in thefurther examples using a 56 MHz spectrometer from Messrs. Japan ElectronOptics Lab. Co. Ltd. at 25° C. with trifluoroacetic acid as an externalstandard, data in ppm), in CHCl₃ :

    ______________________________________                                        2.6:             --CF.sub.3                                                   43.8 to 45.0:    =CF-13 CF.sub.2 --(CF.sub.2).sub.3 --                        47.5:            CF.sub.3 --CF.sub.2 --                                       39.0:            =CF--CF.sub.2 --                                             ______________________________________                                    

EXAMPLE 2

5 g of water and 237.0 g of a mixture of fluorine-containing amines ofthe formula ##STR11## and of the following composition R_(f) = C₅ F₁₁ =41.8% by weight, C₇ F₁₅ = 34.4% by weight, C₉ F₁₉ = 17.7% by weight andC₁₁ F₂₃ = 6.1% by weight are initially introduced into a glass flaskwhich is equipped with a stirrer, reflux condenser, dropping funnel andthermometer, the mixture is heated to about 80° C. and blanketed withnitrogen and 75.06 g of ##STR12## are then added in the course of halfan hour.

The reaction mixture which initially consists of two phases is thenheated up to 120° C., whilst stirring well, and kept at this temperaturefor 2 hours. After cooling, this gives 314 g of a brown, clear, highlyviscous oil, which is very readily soluble in water without a residue(yield: 99.8% of theory). The nuclear magnetic resonance spectra of thesubstance shows the following signals:

¹ H spectrum in d₄ -methanol

    ______________________________________                                         ##STR13##       Doublet with a coupling constant of ˜ 654 Hz           7.6 to 7.9: CH.sub.2 OH                                                                        broad singlet                                                5.7 to 6.7: CFCH triplettized doublet                                          ##STR14##       and HO.sub.2 POCH.sub.2multiplets                             ##STR15##       and CH.sub.2 OH multiplets                                    ##STR16##       singlet                                                       ##STR17##       singlet                                                      ______________________________________                                    

¹⁹ F spectrum in CHCl₃

    ______________________________________                                        30:               --CF.sub.3                                                  39.0:             --CH=CF--CF.sub.2 --                                        43.4 to 44.2      --(CF.sub.2).sub.n --                                       45.0:             --CF.sub.2 --CF=CH--                                        48.0:             CF.sub.3 --CF.sub.2 --                                      ______________________________________                                    

The following further compounds of the general formula I were preparedin accordance with the methods described in Example 1 and 2 (with andwithout solvent).

    __________________________________________________________________________                                                      Reaction                                                                      tempera-                    Sub-                                              ture                        stance                                                                            Starting                                  Reaction                        No. Formula                    materials      Solvent                                                                           time Yield                  __________________________________________________________________________     3                                                                                 ##STR18##                                                                                                ##STR19##     Iso- pro- panol                                                                   3 hours/ 100° C.                                                       nder auto- genous                                                             pressure                                                                           97.5%                   4                                                                                 ##STR20##                                                                                                ##STR21##     Iso- pro- panol                                                                   3 hours/ 100° C.                                                       nder auto- genous                                                             pressure                                                                           97.3%                   5                                                                                 ##STR22##                                                                                                ##STR23##     with- out solvent                                                                 5 hours/ 100°                                                               98.8%                   6                                                                                 ##STR24##                                                                                                ##STR25##     with- out solvent                                                                 2 hours/ 140°                                                               98.8%                   7                                                                                 ##STR26##                                                                                                ##STR27##     with- out solvent                                                                 3 hours/ 140°                                                               98.2%                   8                                                                                 ##STR28##                                                                                                ##STR29##     Iso- pro- panol                                                                   2 hours/ 120° C.                                                       nder auto- genous                                                             pressure                                                                           97.3%                   9                                                                                 ##STR30##                                                                                                ##STR31##     Iso- pro- panol                                                                   4 hours/ 100° C.                                                       nder auto- genous                                                             pressure                                                                           97.6%                  10                                                                                 ##STR32##                                                                                                ##STR33##     Iso- pro- panol                                                                   4 hours/ 100° C.                                                       nder auto- genous                                                             pressure                                                                           97.0%                  11                                                                                 ##STR34##                                                                                                ##STR35##     Iso- pro- panol                                                                   2 hours/ 120° C.                                                       nder auto- genous                                                             pressure                                                                           97.8%                  12                                                                                 ##STR36##                                                                                                ##STR37##     with- out solvent                                                                 4 hours/ 105°                                                               98.2%                  13                                                                                 ##STR38##                                                                                                ##STR39##     Iso- pro- panol                                                                   5 hours/ 80°                                                                98.9%                  14                                                                                 ##STR40##                                                                                                ##STR41##     Iso- pro- panol                                                                   5 hours/ 80°                                                                98.5%                  15                                                                                 ##STR42##                                                                                                ##STR43##     Iso- pro- panol                                                                   5 hours/ 80°                                                                97.2%                  16                                                                                 ##STR44##                                                                                                ##STR45##     Iso- pro- panol                                                                   5 hours/ 80°                                                                98.6%                  17                                                                                 ##STR46##                                                                                                ##STR47##     with- out solvent                                                                 4 hours/ 120°                                                               92.0% (after                                                                  recryst- allization                                                           ) Elementary                                                                  analysis: cal-                                                                found: culated:                                                               C26.3%  26.5% H                                                               1.7% 1.7% N 1.8%                                                              1.7% F60.4%60.4% P                                                            .7% 3.8%               18                                                                                 ##STR48##                                                                                                ##STR49##     with- out solvent                                                                 4 hours/ 120°                                                               94% (after                                                                    recryst- allization                                                           ) cal- found:                                                                 culated: C28.9%                                                               28.3% H 2.3% 1.9%                                                             N 1.4% 1.3%                                                                   F61.0%58.7% P 3.2%                                                            .9%                    19                                                                                 ##STR50##                                                                                                ##STR51##     with- out solvent                                                                 4 hours/ 140°                                                               97.4%                  20                                                                                 ##STR52##                                                                                                ##STR53##     with- out solvent                                                                 5 hours/ 140°                                                               99%                    21                                                                                 ##STR54##                                                                                                ##STR55##     with out solvent                                                                  3 hours/ 120°                                                               98.2%                  __________________________________________________________________________

nuclear magnetic resonance spectra for Examples 3 to 21:

EXAMPLE 3

¹ h spectrum in CDCl₃

    __________________________________________________________________________     12.05 1.62                                                                         ##STR56##            doublet with a coupling constant of ˜629                                Hz                                                 5.6  to      6.6: CFCH     triplettized doublet                               3.7  to                                                                                     ##STR57##    and HO.sub.2 POCH.sub.2 ; multiplets               2.7  to                                                                                     ##STR58##    quartet and broad singlet                          1.0  to                                                                                     ##STR59##    triplet                                            0.9:                                                                                        ##STR60##    singlet                                            __________________________________________________________________________

¹⁹ F spectrum in CDCl₃

    ______________________________________                                        2.9:               --CF.sub.3,                                                38.5:              --CF.sub.2 --CF═                                       42.0 to 44.5       --(CF.sub.2).sub.4 --                                      45.5:              --CF.sub.2 --CF═                                       47.2:               CF.sub.3 --CF.sub.2 --                                    ______________________________________                                    

EXAMPLE 4

¹ h spectrum in 1,1,2-trichloro-1,2,2-trifluoroethane.

    __________________________________________________________________________     11.9 1.5                                                                           ##STR61##            doublet, coupling constant of ˜624 Hz        6.8  to      7.1: CH.sub.2 OH                                                                            broad singlet                                      5.7  to      6.6: CFCH     triplettized doublet                               3.8  to                                                                                     ##STR62##    and HO.sub.2 POCH.sub.2 multiplets                 2.9  to                                                                                     ##STR63##                                                                                   ##STR64##                                         2.6  to      2.7:                                                                           ##STR65##                                                       1.1  to      1.4:                                                                           ##STR66##                                                       __________________________________________________________________________

¹⁹ f spectrum in CHCl₃

    ______________________________________                                        3.5:                --CF.sub.3                                                39.5:               ═CF--CF.sub.2 --                                      43.0 to 45.5:       --(CF.sub.2).sub.n --                                     46.0:               --CF.sub.2 --CF═                                      48.2:                CF.sub.3 --CF.sub.2 --                                   ______________________________________                                    

EXAMPLE 5

¹ h spectrum in CDCl₃ /1,1,2-trichloro-1,2,2-trifluoroethane (1:1)

    __________________________________________________________________________     12.2 1.5                                                                           ##STR67##            doublet, coupling constant 642 Hz                                              broad, indistinct singlet                         5.6  to      6.7: CFCH     triplettized doublet                               3.8  to                                                                                     ##STR69##    multipet                                            3.2  to                                                                                    ##STR70##     superimposing muliplets                           2.5  to                                                                                     ##STR71##    singlet                                            0.87:                                                                                       ##STR72##    singlet                                            __________________________________________________________________________

¹⁹ F NMR spectrum in CDCl₃ /1,1,2-trichloro-1,2,2-trifluoroethane (1:1)

    ______________________________________                                        30:                 --CF.sub.3                                                39.3:               --CF.sub.2 --CF═                                      42.5 to 44.5:       --(CF.sub.2).sub.4 --                                     45.0:               --CF.sub.2 --CF═                                      47.8:               CF.sub.3 --CF.sub.2 --                                    ______________________________________                                    

EXAMPLE 6

¹ h nmr spectrum in CDCl₃ /1,1,2-trichloro-1,2,2-trifluoroethane (1:1)

    ______________________________________                                         12.17 1.55                                                                         ##STR73##               doublet, coupling constant 637 Hz               5.7  to 6.6:   CFCH           triplettized doublet                            3.5  to 4.1:                                                                                  ##STR74##     and CH.sub.2OPO.sub.2 H multliplets             3.2  to 3.5:                                                                                  ##STR75##     multiplet                                       2.75:                                                                                         ##STR76##     singlet                                         0.86:                                                                               ##STR77##                                                                              singlet                                                        ______________________________________                                    

¹⁹ F spectrum in CDCl₃ /1,1,2-trichloro-1,2,2-trifluoroethane (1:1)

    ______________________________________                                        3.0:                 CF.sub.3 --                                              39.4:               --CF.sub.2 --CF═                                      42.5 to 45.0:       --(CF.sub.2).sub.6 --                                     45.5:               --CF.sub.2 --CF═                                      48.0:                CF.sub.3 --CF.sub.2 --                                   ______________________________________                                    

EXAMPLE 7

¹ h nmr spectrum in 1,1,2-trichloro-1,2,2-trifluoroethane

    ______________________________________                                         12.2 1.6                                                                           ##STR78##              doublet, coupling constant 636 Hz                6.8  to 7.4:    C.sub.6 H.sub.5                                                                            multiplet                                        5.4  to 6.4:    CFCH         triplettized doublet                             3.5  to 4.4:                                                                                   ##STR79##   CH.sub.2OP.sub.2 H multiplets                    2.8  to 3.2:                                                                                   ##STR80##   multiplets                                       1.1  to 1.4:                                                                                   ##STR81##                                                                                  ##STR82##                                       ______________________________________                                    

¹⁹ F spectrum in CHCl₃

    ______________________________________                                        2.9:               CF.sub.3 --                                                39.0:             --CF.sub.2 --CF═                                        43.5 to 45.0:     --(CF.sub.2).sub.2 --CF--CF═                            47.7:              CF.sub.3 --CF.sub.2 --                                     ______________________________________                                    

EXAMPLE 8

¹ h spectrum in 1,1,2-trichloro-1,2,2-trifluoroethane

    ______________________________________                                         11.90 1.63                                                                         ##STR83##              doublet, coupling constant 616 Hz                7.4  to 7.9:    OH           broad singlet                                    5.7  to 6.7:    CFCH         triplettized doublet                             3.5  to 4.5:                                                                                   ##STR84##   CH.sub.2 OH and HO.sub.2 POCH.sub.2 superimpo                                 sed multiplets                                   2.7  to 2.8:                                                                                   ##STR85##   singlet                                          ______________________________________                                    

¹⁹ F spectrum in CHCl₃

    ______________________________________                                        3.0:                --CF.sub.3                                                39.0:               ═CF--CF.sub.2 --                                      43.0 to 44.2:       --(CF.sub.2).sub.n --                                     45.0:               ═CF--CF.sub.2 --                                      48.0:                CF.sub.3 --CF.sub.2 --                                   ______________________________________                                    

EXAMPLE 9

¹ h spectrum in 1,1,2-trichloro-1,2,2-trifluoroethane

    ______________________________________                                         12.40 1.51                                                                         ##STR86##               doublet, coupling constant 653 Hz               5.5  to 6.3:   CFCH           triplettized doublet                            3.4  to 4.4:                                                                                  ##STR87##     and CH.sub.2 OP.sub.2 H multiplets              2.4  to 3.0:                                                                                  ##STR88##     quartet                                         1.0  to 1.5:                                                                                  ##STR89##                                                                                    ##STR90##                                      ______________________________________                                    

¹⁹ F spectrum in CHCl₃

    ______________________________________                                        3.4:                --CF.sub.3                                                39.2:               ═CF--CF.sub.2 --                                      43.0 to 45.0:       --(CF.sub.2).sub.4 --                                     48.0:                CF.sub.3 --CF.sub.2 --                                   49.0:               ═CF--CF.sub.2                                         ______________________________________                                    

EXAMPLE 10

¹ h spectrum in 1,1,2-trichloro-1,2,2-trifluoroethane

    ______________________________________                                         ##STR91##                                                                          ##STR92##               doublet, coupling constant 618 Hz               5.8  to 6.8:   CFCH           triplettized doublet                            3.5  to 4.2:                                                                                  ##STR93##     and CH.sub.2 OP.sub.2 H multiplets              2.8  to 3.3:                                                                                  ##STR94##     quartet                                         1.0  to 1.6:                                                                                  ##STR95##                                                                                    ##STR96##                                      ______________________________________                                    

¹⁹ F spectrum in CHCl₃

    ______________________________________                                        2.6:              --CF.sub.3                                                  38.9:             ═CF--CF.sub.2 --                                        43.8 to 45.0:     ═CF--CF.sub.2 --(CF.sub.2).sub.2 --                     47.5:              CF.sub.3 --CF.sub.2 --                                     ______________________________________                                    

EXAMPLE 11

¹ h spectrum in 1,1,2-trichloro-1,2,2-trifluoroethane

    ______________________________________                                         11.85  1.61                                                                        ##STR97##               doublet, coupling constant 614 Hz               7.8  to 8.3:   OH             broad singlet                                   5.70 to 6.70:  CFCH           triplettized doublet                            3.5  to 4.4:                                                                                  ##STR98##     CH.sub.2 OH and CH.sub.2 OPO.sub.2 H                                          superimposing multiplets                        2.7  to 2.8:                                                                                  ##STR99##     singlet                                         1.3  to 1.5    CH.sub.2CH.sub.2CH.sub.2                                                                     multiplet                                       ______________________________________                                    

¹⁹ F spectrum in CHCl₃

    ______________________________________                                        3.0:             --CF.sub.3                                                   39.0:            ═CF--CF.sub.2 --                                         42.5 to 45.5:    --(CF.sub.2).sub.n --CF.sub.2 --CF═                      47.8:             CF.sub.3 --CF.sub.2 --                                      ______________________________________                                    

EXAMPLE 12

¹ h spectrum in CDCl₃ /1,1,2-trichloro-1,2,2-trifluoroethane

    ______________________________________                                         ##STR100##                                                                             doublet with a coupling constant of 636 Hz                          7.8 to 8.2:                                                                             CH.sub.2 OH broad singlet                                           5.7 to 6.8:                                                                             CFCHtriplettized doublet                                            3.8 to 4.4:                                                                              ##STR101##                                                                   HO.sub.2 POCH.sub.2multiplets                                       2.8 to 3.4:                                                                              ##STR102##                                                         2.82:                                                                                    ##STR103##                                                         0.82:                                                                                    ##STR104##                                                         ______________________________________                                    

¹⁹ F spectrum in CDCl₃ /1,1,2-trichloro-1,2,2-trifluoroethane

    ______________________________________                                         3.3:            CF.sub.3 --                                                  38.3:            --CF.sub.2 --CF═                                         42.5 to 45.0:    --(CF.sub.2).sub.4 --CF.sub.2 --CF═                      48.0:            CF.sub.3 --CF.sub.2 --                                       ______________________________________                                    

EXAMPLE 13

¹ h spectrum in CDCl₃

    ______________________________________                                         ##STR105##                                                                             doublet with a coupling constant of 635 Hz                          8.1 to 8.3:                                                                              ##STR106##                                                         3.6 to 4.2:                                                                             CH.sub.2OPO.sub.2 Hmultiplet                                        2.9 to 3.3:                                                                              ##STR107##                                                         2.0 to 3.3:                                                                             CF.sub.2CH.sub.2CH.sub.2unresolved multiplet                        ______________________________________                                    

¹⁹ F spectrum in CHCl₃

    ______________________________________                                         3.1:               --CF.sub.3                                                35.2:               --CF.sub.2 --CH.sub.2 --                                  42.0 to 45.0:       --(CF.sub.2).sub.5 --                                     47.7:               CP.sub.3 --CF.sub.2 --                                    ______________________________________                                    

EXAMPLE 14

¹ h spectrum in CDCl₃

    ______________________________________                                         ##STR108##                                                                             doublet with a coupling constant of 632 Hz                          8.3 to 9.2:                                                                              ##STR109##                                                         3.8 to 4.2:                                                                             CH.sub.2OPO.sub.2 H multiplet                                       2.7 to 3.3:                                                                              ##STR110##                                                         2.0 to ˜3.3:                                                                      CF.sub.2CH.sub.2CH.sub.2unresolved multiplet                        1.2 to 1.5:                                                                             CH.sub.2CH.sub.2CH.sub.2multiplet                                   ______________________________________                                    

¹⁹ F spectrum in CHCl₃

    ______________________________________                                         3.4:               CF.sub.3 --                                               35.3:               --CF.sub.2 --CH.sub.2 --                                  42.0 to 45.5:       --(CF.sub.2).sub.5 --                                     47.8:               CF.sub.3 --CF.sub.2 --                                    ______________________________________                                    

EXAMPLE 15

¹ h spectrum in CDCl₃

    ______________________________________                                         ##STR111##                                                                             doublet with a coupling constant of 633 Hz                          8.8 to 9.4:                                                                              ##STR112##                                                         3.8 to 4.2:                                                                             CH.sub.2OPO.sub.2 H multiplet                                       2.8 to 3.3:                                                                              ##STR113##                                                         2.6 to 2.7:                                                                              ##STR114##                                                         2.1 to 3.2:                                                                             CF.sub.2CH.sub.2broad, unresolved multiplet                         ______________________________________                                    

¹⁹ F spectrum in CDCl₃

    ______________________________________                                         2.6:                CF.sub.3 --                                              34.6:                --CF.sub.2 --CH.sub.2                                    42.0 to 45.0:        --(CF.sub.2).sub.5 --                                    47.2:                CF.sub.3 --CF.sub.2 --                                   ______________________________________                                    

EXAMPLE 16

    ______________________________________                                         ##STR115##                                                                             doublet                                                             6.5 to 7.0:                                                                              ##STR116##                                                         3.8 to 4.2:                                                                             CH.sub.2OPO.sub.2 H multiplet                                       2.9 to 3.4:                                                                              ##STR117##                                                         2.1 to 3.2:                                                                             CF.sub.2CH.sub.3broad, unresolved multiplet                         0.9 to 1.1:                                                                              ##STR118##                                                         ______________________________________                                    

¹⁹ F spectrum in CDCl₃

    ______________________________________                                         2.6:               CF.sub.3 --                                               35.0:               --CF.sub.2 --CH.sub.2 --                                  42.5 to 45.0:       --(CF.sub.2).sub.3 --                                     47.5:               CF.sub.3 --CF.sub.2 --                                    ______________________________________                                    

EXAMPLE 19

¹ h spectrum in CDCl₃

    ______________________________________                                         ##STR119##                                                                             doublet, coupling constant 638 Hz                                   7.0 to 7.5:                                                                             C.sub.6 H.sub.5 unstructured multiplet                              6.6 to 7.0:                                                                             OHbroad singlet                                                     5.4 to 6.5:                                                                             CFCHtriplettized doublet                                            3.5 to 4.4:                                                                              ##STR120##                                                                   CH.sub.2OPO.sub.2 H multiplets                                      2.8 to 3.4:                                                                              ##STR121##                                                         2.5:                                                                                     ##STR122##                                                         1.1 to 1.3:                                                                              ##STR123##                                                         ______________________________________                                    

¹⁹ F spectrum

    ______________________________________                                         2.7:               CF.sub.3 --                                               38.8:               --CF.sub.2 --CF═                                      42.5 to 45.0:       --(CF.sub.2).sub.n --                                     45.5:               ═CF--CF.sub.2 --                                      47.7:               CF.sub.3 --CF.sub.2 --                                    ______________________________________                                    

EXAMPLE 20

¹ h spectrum in CDCl₃ /1,1,2-trichloro-1,2,2-trifluoroethane

    ______________________________________                                         ##STR124##                                                                             doublet with coupling constant of 636 Hz                            3.8 to 4.2:                                                                             CH.sub.2OPO.sub.2 H unresolved multiplet                            2.8 to 3.4:                                                                              ##STR125##                                                                   CH.sub.2 OH unresolved multiplets                                   2.9:                                                                                     ##STR126##                                                         1.1 to 2.5:                                                                             CF.sub.2CH.sub.2CH.sub.2broad, unresolved multi-                              plet, partially super-                                                         ##STR127##                                                         0.8 to 0.9:                                                                              ##STR128##                                                         ______________________________________                                    

¹⁹ F spectrum in CDCl₃ /1,1,2-trichloro-1,2,2-trifluoroethane

    ______________________________________                                         3.2:               CF.sub.3 --                                               35.5:               --CF.sub.2 --CH.sub.2 --                                  42.5 to 45.5:       --(CF.sub.2).sub.4 --                                     48.0:               CF.sub.3 --CF.sub.2 --                                    ______________________________________                                    

EXAMPLE 21

¹ h spectrum in CDCl₃

    ______________________________________                                         ##STR129##                                                                             doublet with coupling constant of 632 Hz                            5.5 to 6.6:                                                                             CFCHtriplettized doublet                                            3.6 to 4.3:                                                                              ##STR130##                                                         2.6 to 3.4:                                                                              ##STR131##                                                         1.1 to 1.5:                                                                              ##STR132##                                                         0.9                                                                                      ##STR133##                                                         ______________________________________                                    

¹⁹ F spectrum in CHCl₃

    ______________________________________                                         3.0:            CF.sub.3 --                                                  38.4:            --CF.sub.2 --CF═                                         42.0 to 45.5:    --(CF.sub.2).sub.n --CF.sub.2 --CF═                      47.3:            CF.sub.3 --CF.sub.2 --                                       ______________________________________                                    

Amongst the fluorinated surface-active agents hitherto known, theampholytic, fluorine-containing esters of phosphorous acid of theformula I, according to the invention, are distinguished by a highsurface-active effectiveness. This is shown by the measured surfacetension values determined in water (see Table No. 1). Here and in thefollowing text, the compounds are compared with the following 6fluorine-containing surface-active agents of the state of the art, whichcontain ester groups of acids of phosphorus and/or quaternary nitrogen:

V1: Ammonium bis-(N-ethyl-2-perfluoro-octyl-sulfonamidoethyl) phosphatewith at most 15% of ammoniummono-(N-ethyl-2-perfluorooctyl-sulfonamidoethyl) phosphate (compare U.S.Pat. No. 2,803,656).

    ______________________________________                                         ##STR134##          (compare DT-OS 1,922,277)                                 ##STR135##          (compare U.S. Pat. Specification 2,759,019)               ##STR136##          (compare U.S. Pat. Specification 3,083,224)               ##STR137##          (compare DT-OS 2,405,042)                                V6: C.sub.6 F.sub.13 C.sub.2 H.sub.4 OPO.sub.3 H.sub.2                                             (compare U.S. Pat.                                                            Specification 3,083,224)                                 ______________________________________                                    

                                      Table No. 1                                 __________________________________________________________________________    Measured surface tension values at 20° C. in mN/m, measured by         the `du Nouy tensiometer method` (draft DIN 53,914)                           in aqueous solution                                                                             F content in                                                Ex- Concentration (g/l)                                                                         the active                                                  ample                                                                             5 1 0.3                                                                             0.1                                                                             0.03                                                                             0.01                                                                             substance                                                                             The product was present as                          __________________________________________________________________________    1   20                                                                              22                                                                              27                                                                              37                                                                              47 60 41.5%   Oil with 100% of active substance                   2   19                                                                              19                                                                              20                                                                              23                                                                              29 45 44.0%   Oil with 100% of active substance                   2a  19                                                                              20                                                                              22                                                                              23                                                                              30 43 44.0%   2 as a solution in isopropanol with                                           50% by weight of active substance                   3   20                                                                              20                                                                              23                                                                              35                                                                              46 53 46.8%   Oil with 100% of active substance                   4   18                                                                              19                                                                              20                                                                              23                                                                              28 34 47.5%   Oil with 100% of active substance                   5   17                                                                              18                                                                              22                                                                              33                                                                              48 59 50.1%   Oil with 100% of active substance                   6   19                                                                              20                                                                              25                                                                              35                                                                              55 56 52.7%   Oil with 100% of active substance                   7   21                                                                              24                                                                              28                                                                              32                                                                              37 46 37.3%   Oil with 100% of active substance                   8   18                                                                              18                                                                              20                                                                              22                                                                              33 47 48.7%   Oil with 100% of active substance                   11  16                                                                              17                                                                              19                                                                              21                                                                              29 37 47.5%   Oil with 100% of active substance                   19  18                                                                              19                                                                              21                                                                              23                                                                              30 44 41.3%   Oil with 100% of active substance                   20  --                                                                              20                                                                              22                                                                              24                                                                              29 43 44.8%   Oil with 100% of active substance                   V1  22                                                                              --                                                                              47                                                                              48                                                                              62 63 21%, relative                                                                         36% strength by weight solution in                                    to the solution                                                                       isopropanol/water                                   V2  22                                                                              23                                                                              35                                                                              46                                                                              56 57 49.8%   100% of active substance                            V3  18                                                                              18                                                                              19                                                                              21                                                                              25 33 41.1%   100% of active substance                            V4  27                                                                              31                                                                              43                                                                              54                                                                              66 -- 22.4%, relative                                                                       34.5% by weight in 1:1 isopropanol/water                              to the solution                                             V5  20                                                                              21                                                                              24                                                                              35                                                                              42 46 11.6%, relative                                                                       19.9% by weight in isopropanol/water                                  to the solution                                             __________________________________________________________________________

A further interesting property of the compounds according to theinvention is their foaming behaviour (Table No. 2). The foam formationtest according to Ross-Miles shows that, in the compounds according tothe invention, the foaming power can be controlled by the chain lengthof the perfluoroalkyl radical. In addition to the weak foamers No. 1 andNo. 7 having C₅ F₁₁ radicals, there are the strongly foaming productsNo. 3 and No. 4 having C₇ F₁₅ radicals. The product No. 2 or 2a withmixtures of perfluoroalkyl chains of C₅ -C₁₁ shows a medium foamingbehaviour. The foaming power can be increased by omitting branches atthe methyl groups adjacent to the phosphite group (comparison betweencompounds No. 8 and No. 2). As a result of their different foamingbehaviour, the fluorinated surface-active agents according to theinvention are available as tailor-made products for variousapplications. Thus, strongly foaming surface-active agents are employedfor cleaning agents, whilst weak foamers having good values for loweringthe surface tension are employed in aqueous phase for degreasing metalparts in electroplating lines.

    ______________________________________                                        Foam height (mm) at                                                           25° C.         70° C.                                           Example 0 minutes  5 minutes  0 minutes                                                                             5 minutes                               ______________________________________                                        1       10         0          10      0                                       2       75         70         30      25                                      2a      65         65         85      85                                      3       150        140        80      30                                      4       50         50         35      35                                      5       190        190        240     240                                     6       90         90         160     160                                     7       10         0          10      0                                       8       150        140        160     160                                     11      180        180        220     220                                     V1      0          0          5       0                                       V2      240        240        200     190                                     V3      100        100        260     260                                     ______________________________________                                    

Due to their surface properties, the ampholytic fluorinated phosphitesaccording to the invention are widely used as surface-active agents inthe textile industry for wetting and cleaning. Table No. 3 describes thewetting power of the products according to the invention towards cottonand wool in an aqueous system. The determination was carried out inaccordance with an immersion wetting test in the following manner:

Determination of the immersion wetting power:

A disc (about 35 mm φ) of the test fabric is introduced into the testsolution (600 ml beaker, tall type) by means of an immersion clamp insuch a way that it is held about 30 mm above the bottom and 40 mm belowthe surface of the liquid. The disc sinks to the bottom when the air hasbeen displaced from the fabric. The time from the immersion to the startof sinking is measured by means of light beams which are connected to aswitch box (Viscomatik instrument). The pair of light beams is arrangedin such a way that the determination of time corresponds to the DIN53,901 method.

    ______________________________________                                        Sinking time (seconds)                                                        Cotton                     Wool                                               Example 25° C.                                                                           50° C.                                                                            70° C.                                                                         25° C.                            ______________________________________                                        1       175       165        75      13                                       2       145       100        60      18                                       3       180       130        80      17                                       4       >300      235        95      8                                        5       105       90         65      18                                       6       >300      155        75      6                                        7       >300      >300       180     25                                       8       135       165        95      14                                       9       115       75         50      17                                       11      45        30         25      7                                        19      50        40         12      6                                        V1      >300      >300       >300    >300                                     V2      270       135        65      7                                        V3      300       165        45      13                                       ______________________________________                                    

Due to their good wetting power, the compounds according to theinvention can be used as dry-cleaning detergents. Dry-cleaningdetergents are interface-active substances which enhance the cleaningaction of organic solvents and broaden this action since hydrophilicsoilings are also dealt with as the result of incorporating water intothe organic medium. Table No. 4 shows the results of cleaningexperiments in perchloroethylene. The cleaning experiments were carriedout in the following manner:

Description of the procedure in the cleaning experiments:

Four series of artificially soiled standard test fabrics, in each casecotton, wool, polyester fabric and polyacrylonitrile fabric,manufactured by Testfabrics Inc. Middlesex, Ill. (USA) (soiling: ironoxide, carbon black, starch and oil) are successively cleaned in thesame cleaning liquor in the laboratory. Cleaning is carried out in 400ml of perchloroethylene liquors on fabrics which were conditionedbeforehand under the action of atmospheric humidity in order to producecomparable conditions, corresponding to the so-called Lini test (inanalogy to DIN Standard 54,024). The concentration of the fluorinatedsurface-active agents is 0.5 g/l and the temperature is 30° C.

The cleaning action is determined as % brightening in accordance withthe formula

    A = 100 · (Wg - Wa)/(Wo - Wa)

Wo = reflectance of the unsoiled original fabric

Wg = reflectance of the soiled fabric

Wa = reflectance of the soiled fabric after cleaning

The graying of the unsoiled original fabric, also treated, is determinedin accordance with the formula

    V = 100 · (Wo - Wv)/Wo

Wo = reflectance of the unsoiled original fabric

Wv = reflectance of the cleaned sample

On the basis of the brightening and graying values obtained, theproducts according to the invention are superior to the comparativeproducts V2 and V6.

The compounds of the formula I, according to the invention, are alsosuitable for use as additives to fire-fighting agents based on syntheticfoam, in particular in combination with other fluorine-containingsurface-active agents.

                                      Table 4                                     __________________________________________________________________________    Results of the cleaning experiments in perchloroethylene with various         fluorinated surface-active agents (test fabrics conditioned, before           cleaning, for 24 hours at 80% relative atmospheric humidity and               20° C.). B = Brightening, G = Graying                                            Perchloro-                                                                            Product                                                                             Product                                                         ethylene                                                                              from  from  Product                                                                             Product                                             without additive                                                                      Example 1                                                                           Example 2                                                                           V2    V6                                                  % B % G % B                                                                              % G                                                                              % B                                                                              % G                                                                              % B                                                                              % G                                                                              % B                                                                              % G                                    __________________________________________________________________________    Series I.                                                                     Cotton    2   1.9 3  2.3                                                                              4.7                                                                              1.2                                                                              6.5                                                                              7  0.4                                                                              10.9                                   Wool      5.8 0.0 10.8                                                                             0.8                                                                              15.8                                                                             0.4                                                                              0  18 10.5                                                                             5.3                                    Polyester fabric                                                                        5.5 0.7 4.4                                                                              1.9                                                                              6.4                                                                              1.1      5  2.0                                    Polyacrylonitrile                                                             fabric    5.0 3.3 6.5                                                                              5.2                                                                              8.1                                                                              3.4      4.2                                                                              7.7                                    Series II.                                                                    Cotton    3   4.7 2.6                                                                              3.7                                                                              4.5                                                                              1.3                                                                              1.0                                                                              16 0.4                                                                              11                                     Wool      5   2   10 3  15.2                                                                             0.6                                                                              3.0                                                                              12 10 10.8                                   Polyester fabric                                                                        6   1.5 3  2.6                                                                              5.9                                                                              1.7      4.8                                                                              3.8                                    Polyacrylonitrile                                                             fabric    6.1 2.9 5.5                                                                              3.2                                                                              7.7                                                                              3.5      4.1                                                                              8.3                                    Series III.                                                                   Cotton    3.1 5.5 2.7                                                                              5.4                                                                              4.8                                                                              1.7                                                                              2.5                                                                              12 1.8                                                                              13.8                                   Wool      5.8 0   11.7                                                                             3.3                                                                              15.6                                                                             0.7                                                                              10.0                                                                             12.2                                                                             11.1                                                                             12.2                                   Polyester fabric                                                                        5   4.1 3.5                                                                              5.1                                                                              5.7                                                                              2.0      3.4                                                                              3.7                                    Polyacrylonitrile                                                             fabric    5.3 4.8 5  6.1                                                                              7.5                                                                              3.9      5  9.7                                    Series IV.                                                                    Cotton    3   7.1 2.6                                                                              8  4.2                                                                              2.3                                                                              1  13 0.8                                                                              13.4                                   Wool      5.9 1.1 10.6                                                                             2.7                                                                              15.1                                                                             1.0                                                                              9.0                                                                              1.5                                                                              13.1                                                                             11.8                                   Polyester fabric                                                                        5.6 4.8 3.5                                                                              6.7                                                                              5.5                                                                              2.8      4.5                                                                              8.8                                    Polyacrylonitrile                                                             fabric    5.0 5.7 5  5.4                                                                              7.8                                                                              3.6      4.5                                                                              10.1                                   __________________________________________________________________________

What is claimed:
 1. Ampholytic, fluorine-containing esters ofphosphorous acid of the general formula ##STR138## in which R_(f)represents a perfluoroalkyl radical having 3 to 16 C atoms, R₁ and R₂which can be identical or different represent hydrogen atoms,short-chain alkyl radicals having 1 to 4 C atoms, cyclohexyl radicals,2-hydroxyalkyl radicals or the radical R_(f) --(CF═CH)_(m) --(CH₂)_(p)-- and Q represents alkylene radicals --(CH₂)_(x) -- with x = 2 or 3 andalkylene radicals --CH₂ CHR-- or --CH₂ CRR'--CH₂ with R and R' being ashort-chain alkyl radical or a phenyl radical, it also being possiblefor R' to be H, and in which, furthermore, m is 0 or 1 and p is aninteger from 1 to 4.